BENEFICIATION OF LOW GRADE LIMESTONE

FROM ACC MINES, MADUKKARAI, COIMBATORE DISTRICT, TAMILNADU.

B.P.Ravi*, V.Rampur, P.S.Kumar, S.J.G.Krishna,C.Rudrappa andG.Shyla
Mineral Processing Department, VSKU PG Centre, Nandihalli 583119
*
Email;ravibelavadi@gmail.com

ABSTRACT
A low gradeLimestone from ACC mines, Madukkarai, Coimbatore district, Tamil
Naduwas subjected to beneficiation by cationic reverse flotation process with the aim of
producing cement grade and metallurgical grade concentrates. The low grade limestone analyzed
45% CaO, 80%TC, 18% SiO 2, 1.3% MgO, 1.30% Fe2O3, 2.50% Al2O3, 0.33% alkalis and
36.00% LOI. It contained mainly calcite and quartz which were mutually inter grown with fair
degree of liberation at 65 mesh size. Reverse cationic flotation was preferred to direct soap
flotation as practiced in beneficiation plant at Madukkarai. Inverse flotation studies were carried
out to float siliceous impurities using cationic collectors varying collector type, collector dosage,
mesh of grind and pulp density. Cement grade composite concentrate ( non-float and slimes)
assaying 9.51% AI, 90% Total carbonates at wt.% yield of 88 by a process comprising of
grinding to MOG D80 400 microns, desliming/ screening over 400 mesh, rougher conditioning
with 0.4kg/t SOKEM565C for 2minutes at 50%S, rougher flotation for 4 minutes, at pH 8 and
28%S. The float of -16+400 mesh sand fraction assaying 80.30% AI, 18% total carbonates may
be used as eco sand.On the contrary, premium metallurgical grade concentrate assaying 54.64%
CaO, 0.6% SiO2, 0.7% MgO, 1.4% Fe2O3, 0.7% Al2O3, 41.0% LOI with weight % yield of 55.2,
could be produced at20% solids, MOG D 80 400 microns, and pH 8 with 1.0 kg /t of SOKEM 565
C. The evolved nil waste process is stable, selective, and easily adaptable in the existing anionic
soap direct flotation plant at ACCMadukkarai cement works, yielding valuable products.
Key words;flotation, cationic collectors, limestone flotation, cement and metallurgical grades.
INTRODUCTION
Limestone is used mainly in cement industry (69%) followed by metallurgical
industries(12%), like, iron-& steel as fluxes, in agriculture as soil conditioner(10%) and
manufacturing industries (9%), like, glass making, paper, water purification, filler in plastics
(IBM (2013)) The specification for limestone for metallurgical industry is CaO > 48%, SiO 2<
1.5% , Al2O3< 1%, Fe2O3<2%, MgO<1%, Na2O + K2O < 0.5%, P<0.1% and S<0.1%. The
specification of limestone for cement industry isCaO> 45%, Total carbonates > 80%,SiO 2<12%,
MgO<3%,Fe2O3<5% ,<5 % +0.25 mm and ~ 30% + 0.09 mm (BIS : 10345– 2009).
Madukkarai is located 2.50 km away from Madukkarai Cement Works, which lies 10 km
from Coimbatore. Geographically the mining lease area (ML3) fall between the latitude 10° 55’
to 10° 56’ and longitude 76° 56’ to 76° 59’. The topography is gently undulated and surrounded
by Calc – granulites hills. Country rock is garnetiferous sillimanite schist in most of the places, at
places the limestone also occurs in association with charnockite and calc gneiss.Limestone bands
of varying width are well exposed in roadside west block with intervening calc granulite bands.
The limestone is greyish white and light to dark grey in colour, crystalline and coarse to fine
grained in nature. It is generally observed that at the contact zone with calc granulite, the
limestone is pink in colour. The limestone commonly shows inclusion of diopside, biotite,
muscovite and graphite. Limestone bands are separated by calc granulite and at places there are
thin lenses of calc granulite within the limestone band itself. Intrusions of pegmatite and
occasional thin quartz veins are common within limestone. Occurrence of clay within the
limestone is commonly observed. Since, 1965, ACC is mining low grade limestone by opencast
mining method and is partly beneficiating to sweeter grade limestone for blending and using it
with raw mix.It has a 4000 tpd cement manufacturing based on semi-wet process. Concentrate
produced in the flotation plant assaying 83% total carbonate is the feed to the cement
kiln.Limestone up gradation process comprised of multistage crushing, grinding and flotation. The
flotation plant is operated in two parallel lines at a rated capacity of 60-65 tph per line.
Limestone received in the cement works from Madukkarai mine and +15mm fraction from
Walayar mine in1:1 ratio is mixed, crushed and screened at site in jaw and impact crushers to all
–15mm size. This blend assaying 76-77% Total Carbonates forms the feed to two ball mills
operated in close circuit with 350mm hydrocyclones. Overflow from the hydrocyclone is
deslimed in a cluster of 100mm hydrocyclones. The overflow joins the concentrate thickener
whereas the underflow constitutes the feed to flotation. Flotation is carried in two parallel
batteries, one of Dorr-Oliver make and other of Outokumpu make equipped with automatic level
controller. Process flowsheet is given in figure1. Each flotation battery has 12 cells. First 8
cells produce concentrate and last 4 cells are used as scavenger cells. The scavenger concentrate
is fed back to the conditioner, whereas the scavenger tails forms the final rejects. The
concentrate joins the thickener. Thickener underflow assays around 83% Total Carbonates and is
the feed to cement kiln. The reject assays around 25-30% Total Carbonates. Anionic collector
used in the flotation is a mixture of soap, resin and caustic. The reagents consumption is 1 kg/t
of ROM and is partly added in the conditioner and remaining in the various flotation cells.
Though lot of work has been carried out on direct flotation of limestone from the study
area( Sutone et.al,(2004) and Shandilya and Jha(2012)), little work has been done on inverse
flotation of limestone in general except the works of Rao et.al.(2009),Vijayakumar et.al.
(2003and2009) for cement gradeand Rachappa Kadli et.al.(2014and2015) for metallurgical grade
limestone.Hence, the aim of the present work was to beneficiate low grade limestone to cement
and metallurgical grade.

Fig.1; ACC Madukkarai ProcessFlow Chart

EXPERIMENTAL

Material and Methods; Lime stone samples of 200 kgs was collected from Lime stone mining
area of ACC mines,Madukkarai, Coimbatore district, Tamil Nadu. The flotation regents were
collected from M/s Somu organics Ltd., Bangalore. The as received sample was stage crushed to
-10 mesh using primary lab jaw crusher[150 x225mm – 25 mm set], lab roll crusher [200mm x
150mm] 300 mmx600mm 16 mesh screen. The crushed sample was subjected to standard feed
preparation by adopting sampling procedures. The sample was ground at 67%S in 175mm x
350 mm rod mill 5 kg rod charge -10 Nos. of 40mm, 25mm and 20mm dia., varying grinding
time. The ground pulp was subjected to froth flotation using D12 Denver type MPE lab sub
aeration flotation machine. The feed and products after dewatering followed by drying were
weighed, sampled and subjected to characterization studies. MOG, Kinetics, Choice of collector,
Collector dosage and % solids were varied.

RESULTS AND DISUCUSSIONS

Characterization studies; The whitish gray coloured limestone sample had bulk density of
1.81t/m3 and 350 angle of repose. The work index of the sample was found to be 11.5 KWh/short
ton. The sample contained fine grained calcite intimately associated with minor amounts of fine
grained aggregates of quartz, iron oxides, clay and trace amounts of feldspar. The sample was
siliceous low grade granular limestone with fair degree of liberation at -65 mesh size. The
sample analyzed 41% CaO, 18%SiO2, 1.23% MgO, 1.30% Fe2O3, 1.50% Al2O3, 0.33alkalis 80%
total carbonates and 36% LOI. The diagnostic amenability test on -65 mesh sample involving
sink and float test at 2.8 specific gravity were conducted and observed 5%acid insolubles in sink
and slimes assayed 10% acid insoluble.
-16 mesh samples were ground in rod mill for varying time from 5 to 15 minutes and
samples were subjected to size analysis. The data is given in Table 1. The grindability data
indicated that the sample was medium soft in nature
Table: 1 Size analysis of rod mill grindability
Conditions:
250 gms of – 16 mesh ground in 175mm x 350mm rod mill with 5 kg rod charge at 67%
S for time varying from 0/5/10/15minutes
Mesh size Wt % retained
Mesh
in microns 0’ 5’ 10’ 15’
-16+22 1000 10.0 1.6 0 0
-22+30 818 12.0 5.6 0 0
-30+52 600 38.0 27.2 2.4 3.2
-52+72 300 15.0 19.2 15.2 1.6
-72+120 212 8.0 20.0 28.8 28.8
-120+200 125 5.0 8.0 15.2 23.2
-200+277 75 4.0 5.6 8.8 13.6
-277+400 54 6.0 1.6 3.2 3.2
-400 38 2.0 11.2 26.4 26.4
100.0 100.0 100.0
D 80 microns 730 400 200 150
Effect of mesh of grind [MOG]:Inverse flotation tests were conducted varying mesh of
grinding time 5’/10’/15’ with respective D80 400/200/150 microns respectively at natural pH of 8,
with 1 Kg/t anionic collector SOKEM 565 C. The results have been tabulated Table -2 and
graphically represented in figure 2.The results indicated that the grade of silica content reduced
to a minimum at mesh of grind of 400 microns and hence was chosen. The fall in grade in coarse
grind of 150 microns was due to lack of liberation of silica values while the fall in grade in very
fine grind of 200 microns was attributed to interference of slimes. Rao et.al.(2009), Vijayakumar
et.al.(2009) and RachappaKadli et.al. (2015) obtained optimum MOG at grinds finer than 150
microns. Incidentally the present direct soap flotation process at Madukkarai plant employs a
finer grind of 105 microns. From the experimental studies, it has been concluded that with mesh
of grind of 5’ D80 at 400 microns results obtained are encouraging.

Table-2: Effect of MOG on inverse flotation

Conditions; Mesh of grind 5’/10’/15’has D80 400/200/150microns Flotation pH 8, % S 19,
Stage Cell Rpm Reagent Dosage kg/t CT min FT min
RF 250 1200 SOKEM 565C 1 2 4
Results:
Acid insoluble %
Mesh of grind Product Wt%
Assay Distn
Float reject 40.8 41.60 98.2
5’ Non float 59.2 0.60 1.8
D80 400 microns Head Cal 100.0 18.40 100.0
Float reject 44.8 33.43 98.0
10’ Non float 55.2 0.68 2.0
D80 200microns Head Cal 100.0 18.83 100.0
Float reject 59.2 31.10 97.8
15’ Non float 40.8 1.00 2.2
D80 150microns Head cal 100.0 18.79 100.0

Fig.2: Effect of MOG on inverse flotation Fig.3: Effect of MOG on rate constant

Effect of kinetics;Kinetics of inverse flotation was carried out using 1 kg/t SOKEM 565 C
cationic collector for time intervals of 0.25, 0.5, 1.0,2.0 and 4 minutes flotation time varying the
MOG from D80 400, 200 and 150 microns by varying grinding time (5,10 and 15 minutes).The
results indicated that the kinetics of inverse flotation varying MOG followed first order equation.
The results also showed that increase in coarseness of the MOG increases the flotation rate
constant of siliceous gangue flotation with maximum at D80200 microns. The distribution of %
AI increased with increase in coarseness of grind. Nikkam Suresh (2002) indicated that the
water content, slime % increases with increase in slime content of MOG during anionic flotation
of limestone. The results are shown in figure 3.
Choice of collector: Inverse flotation tests were conducted at D 80 size of 400 microns varying
collectors like SOKEM 565C, SOKEM 524C, SOKEM 522C and SOKEM 503C and
maintaining dosage of 1 kg/t. The results are shown inTable 3. The results indicated that
SOKEM 565C was more selective in flotation of siliceous gangue. Incidentally obtained similar
results with SOKEM 565C in case of reverse flotation of low grade limestone to get cement
grade concentrate was obtained by Rao et. al (2009), Vijayakumar et.al.(2009) and
RachappaKadli et.al (2015).
Table-3: Choice of collector on flotation
Conditions; Mesh of grind 5’ D80 400microns, Flotation pH 8, and % S 19
Stage cell Rpm Reagent Dosage kg/t CT min FTmin
RF 250 1200 SOKEM565C/524C/522C/503C 1 2 4
Results:
Collector Product Wt% Acid insoluble %
Assay Distn
Float reject 50.8 41.60 98.2
SOKEM Non float 49.2 0.60 1.8
565C Head Cal 100.0 18.96 100.0
Float reject 47.2 44.20 90.4
SOKEM Non float 52.8 4.20 9.6
524CC Head Cal 100.0 23.09 100.0
Float reject 46.4 39.50 88.1
SOKEM Non float concentrate 53.6 4.60 11.9
522C Head Cal 100.0 20.78 100.0
Float reject 46 33.10 88.4
SOKEM Non float concentrate 53.6 3.80 11.6
503C Head Cal 100.0 17.56 100.0

Effect of pulp density on flotation:Flotation tests were conducted varying % of solids from
20/47. Increase in % of solids though increases yield, but reduces selectivity.Tests were
conducted by varying pulp density 19/33/47 % S. The results are given in Table-4. Incidentally
similar results were obtained by Rao et.al(2009) by working on flotation of low grade limestone
samples of Andrapradesh. This may be attributed to better dispersion of air bubbles in the pulp
and better dropping of entrapped silica in the froth. But to obtain low silica metallurgical grade
concentrate 20 % solids seems to be optimum.Shandilya and Jha (2012) while working in ACC
Madukkarai flotation plant opined that 20-24% S was found optimum for maximum selectivity,
total carbonate recovery and productivity.
 Table4: Effect of %S on inverse flotation
Conditions; MOG D80 400 microns, pH 8, SOKEM 565C dosage 0.4kg/t, % S 19/33/47
Stage Cell Rpm Reagent Dosage kg/t CT min FT min
RF 250 1200 SOKEM 565C 0.4 2 4

Acid insoluble %
%S Product Wt%
Assay Distn
Float reject 32.8 41.30 75.2
19 Non float concentrate 67.2 6.60 24.8
Head Cal 100.0 18.10 100.0
Float reject 26.4 40.68 40.7
33 Non float concentrate 73.6 10.00 59.3
Head Cal 100.0 18.10 100.0
Float reject 20.0 24.06 25.9
47 Non float concentrate 80.0 17.18 74.1
Head Cal 100.0 18.55 100.0

Fig 4[a]; Effect of %Solids on Wt.% yield Fig4[b]; Effect of %Solids on% AI assay
Collector dosage variation: Tests were conducted at D80 size of 400 microns by varying
collector SOKEM 565C dosage from 0.4 to 1.2kg/t. The results are shown in Table 5.Result
indicated that the increase in collector dosage decreased Wt % yield and % AI grade (except at
1.2kg/t dosage) with a best result at 1.0 kg/t. Rao et.al (2009) obtained optimum results at 0.6kg/t
SOKEM 565C for cement grade concentrate. RachappaKadli et.al. (2015) produced
metallurgical grade concentrate with 1.0 kg/t SOKEM 565 C. Hence, to produce cement grade
concentrate 0.4 kg/t of collector is sufficient to float less gangue while to produced metallurgical
grade concentrate with low silica 1.0 kg/t of collector may be required to remove siliceous
gangue which is logical.
 Table-5: Effect of collector SOKEM565C Dosage variation
Conditions; Mesh of grind 5’, D80 400microns, Flotation pH 8, and % S 19
Stage Cell Rpm Reagent Dosage kg/t CT min FTmin
RF 250 1200 SOKEM 565C 0.4/0.6/0.8/1.0/1.2 2 4
Results;

SOKEM565C Acid insoluble %

Product Wt%
dosage kg/t Assay Distn
Float reject 32.8 41.30 75.2
0.4 kg/t Non float 67.2 6.60 24.8
Head Cal 100.0 18.00 100.0
Float reject 47.2 35.00 92.1
0.6 kg/t Non float 52.8 2.70 7.9
Head Cal 100.0 17.90 100.0
Float reject 48.8 34.30 92.9
0.8kg/t Non float 51.2 2.50 7.1
Head Cal 100.0 18.00 100.0
Float reject 50.8 41.60 98.2
1.0 kg/t Non float 49.2 0.60 1.8
Head Cal 100.0 18.96 100.0
Float reject 56.8 31.00 98.8
1.2kg/t Non float 43.2 0.90 2.2
Head Cal 100.0 18.00 100.0

Fig 5[a]: Effect of SOKEM565Ckg/t on Wt% yieldFig 5[B]: Effect of SOKEM565Ckg/t on % AI grade
Final test under optimum conditions: Test under optimum conditions of 20% solids, MOG D 80
400 microns, natural pH 8, collector conditioning time of 2 minutes and flotation time of 4
minutes in each stage with 0.4 kg/t SOKEM 565C in I stage and 0.6kg/t SOKEM 565C in II
stage for floating the residual silica in I stage non float were conducted. The results are given in
Table 6.The I stage flotation with 0.4 kg/t collector produced concentrate assaying 52.00% CaO,
6.6% SiO2, 1.17% MgO, 1.7% Fe2O3, 1.0% Al2O3, 37.0% LOI with weight % yield of 67.2,
meeting the cement grade specifications. The 2 stage flotation with 1 kg/t collector produced a
concentrate assaying 54.64% CaO, 97%TC, 0.6% SiO 2, 0.7% MgO, 1.4% Fe2O3, 0.7% Al2O3,
41.0% LOI with weight % yield of 55.2 meeting the metallurgical specification.
Table 6 – Result of final test under optimum conditions
Conditions; MOG D80 400 microns, pH 8, SOKEM 565C dosage 1.0kg/t, % S 20
Stage Cell Rpm Reagent Dosage kg/t CT min FT min
RF1 250 1200 SOKEM 565C 0.4 2 4
RF2 250 1200 SOKEM 565C 0.6 2 4
Results;
Product Wt% Acid insoluble %
Assay Distn
RF1 reject 32.8 41.38 75.4
RF2 reject 8.0 51.30 22.8
NF2 (Met grade conc) 59.2 0.60 1.8
Head Cal 100.0 18.00 100.0
RF1+RF2 reject 40.8 39.45 98.2
NF2+RF2 Cal (Cem grade conc) 67.2 6.60 24.6

Final test for cement grade concentrate production; The test comprised of grinding the
sample to MOG D80 400 microns, desliming/ screening over 400 mesh, rougher conditioning
with 0.4kg/t SOKEM565C for 2minutes at 50%S, rougher flotation for 4 minutes at pH 8 and
28%S. The non-float and slimes constituted the final concentrate. The test was carried out to
simulate the industrial condition. The results are given in Table 7. The results indicate that a
composite of slime and deslimed non float yielded a cement grade assaying 9.51% AI,90% Total
carbonates at wt% yield of 88.The concentrate size was coarse [D 800.3mm] w.r.t. ACC
concentrate[D800.2mm]. The non-floatsand fraction assaying 80.30% AI, 18% total carbonates
may be used as eco sand. Incidentally, Shandilya (2012) recommended the flotation rejects as
ACC eco sand for plastering and concrete works.The above desliming- inverse flotation nil
waste process appears to be stable, easily adaptable at site,- producing raw materials for civil
construction like ACC Eco sand as an alternative to river sand and cement grade limestone .
Table 7 – Result of final test simulating plant conditions
Conditions; MOG D80 400 microns, wet screening over 400 mesh for removing slimes in
-400 mesh fraction , + 400 mesh sand subjected to flotation.
Stage Cell Rpm Reagent Dosage CT FT
kg/t %S min %S min
RF 250 1200 SOKEM 565C 0.4 50 2 28 4
Results;
Product Wt% Acid insoluble %
Assay Distn
-400 mesh slimes conc. 12.0 12.00 8.0
Non float conc. 76.0 9.12 38.5
Float reject 12.0 80.30 53.5
Head Cal 100.0 18.00 100.0
-400#+RNF Conc (Cem grade) Cal 88.0 9.51 46.5
CONCLUSIONS
A low grade Limestone from ACC mines, Madukkarai, Coimbatore district, Tamilnadu
assaying 45% CaO, 80% TC, 18% SiO2, 1.3% MgO, 1.30% Fe2O3, 2.50% Al2O3, 0.33% alkalis
and 36.00% LOI yielded a cement grade composite concentrate ( non-float and slimes) assaying
9.51% AI, 90% Total carbonates at wt% yield of 88 by a process comprising of grinding to MOG
D80 400 microns, desliming/ screening over 400 mesh, rougher conditioning with 0.4kg/t
SOKEM565C for 2minutes at 50%S, rougher flotation for 4 minutes at pH 8 and 28%S.The float
of -16+400 mesh sand fraction assaying 80.30% AI, 18% total carbonates may be used as eco
sand.The evolved nil waste process is stable, selective, and easily adaptable in the existing
anionic soap direct flotation plant at ACC Madukkarai cement works. Alternatively,a
premiummetallurgical grade concentrate assaying 54.64%CaO, 97%TC, 0.6% AI, 0.7% MgO,
1.4% Fe2O3, 0.7% Al2O3, 41.0% LOI with weight % yield of 55.2, could be produced at MOG
D80 400 microns, 19%Solids with1.0 kg/t of SOKEM 565 C. The low grade siliceous crystalline
limestone from Madukkarai is amenable to inverse flotation process. Detailed tests for process
confirmation and data generation for conceptual design are recommended.
ACKNOWLEDGEMENTS
The authors are thankful to M/s ACC Ltd(Madukkarai) and SOCL, Bangalore for arranging the
limestone and reagent samples respectively.
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